CN108002996A - A kind of preparation method of medicine intermediate beta-diketone compound - Google Patents
A kind of preparation method of medicine intermediate beta-diketone compound Download PDFInfo
- Publication number
- CN108002996A CN108002996A CN201810019861.2A CN201810019861A CN108002996A CN 108002996 A CN108002996 A CN 108002996A CN 201810019861 A CN201810019861 A CN 201810019861A CN 108002996 A CN108002996 A CN 108002996A
- Authority
- CN
- China
- Prior art keywords
- formula
- beta
- reaction
- preparation
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
Abstract
The present invention provides a kind of preparation method of medicine intermediate beta diketone compound, the described method includes：II ester compounds of I ketone compound of formula and formula, in organic solvent, in the presence of basic catalyst, reaction obtains III beta diketone compound of formula, R1‑CO‑CHR2R3Formula I, R4‑CO‑OR5Formula II, R1‑CO‑C(R2R3)‑CO‑R4Formula III, this method can effectively improve the selectivity and reaction yield of product, and reaction yield can reach 72.4%, while reduce the difficulty of post-reaction treatment, reduce the pollution to environment, reduce production cost, improve the economic efficacy and security of production.
Description
Technical field
The present invention relates to a kind of preparation method of medicine intermediate dione compounds, more particularly to it is a kind of in high yield
Beta-diketone compound preparation method.
Background technology
Beta-diketone compound is a kind of important compound, it is frequently as the important synthesis unit in organic synthesis to build
Other medicines compound or functional material.Beta-diketone compound is also a kind of compound with extensive use, such as can be used
In METAL EXTRACTION and polymer stabilising.Therefore, the synthetic methods of the cyclohexadione compounds great reality in pharmaceutical production is studied
Meaning, has chemical and field of medicaments very big value.
Method using Claisen condensation is the generally known method for preparing beta-diketone compound.
1- cyclopropyl -1,3- diacetyl is the important intermediate of synthesizing fungicide cyprodinil.J. Org. Chem, 17,
685,1952 document reports are reacted in the presence of hydrogenate soda and prepared with cyclopropyl methyl ketone and acetic acid ethyl reaction,
US3507958 is also reported with cyclopropyl methyl ketone and acetic acid ethyl reaction, is reacted and is prepared in the presence of soda is hydrogenated, above two
It is 40-75 % that product prepared by method, which produces its yield, and the content of product is 75-82%, it is impossible to meets the matter of synthesis cyprodinil
Amount requires.And the sodium hydride and Sodamide used is inflammable, it is unfavorable for wide scale security production.
EP-A-0410726 reports react system with cyclopropyl methyl ketone and acetic acid ethyl reaction in the presence of methanol soda
Standby 1- cyclopropyl -1,3- diacetyl, yield is only 21%, and product purity is only 75%.1- cyclopropyl -1,3- fourths prepared by this method
Diketone cannot equally meet the quality requirement for synthesizing cyprodinil.
3,5- heptadione are the key intermediates for synthesizing 3,5- heptandiols.Oneself has document report preparation 3,5- heptadione
Method, but this method yield is relatively low, and production operability is not strong.Wherein, ZhurnalObshcheiKhimil, 28,2845
~ 6,1958 report malonyl chloride reacts to obtain the 3,5- heptadione products that yield is 51% with grignard reagent E tMgBr.Should
Method must react under -70 DEG C of extremely low temperature, and processing is extremely difficult, is difficult to realize in industrial practice.
CN1636422A is reported by using Claisen condensation method, makees catalyst with potassium tert-butoxide, using DMF as solvent system
Standby 2,2,6,6- tetramethyl -3,5 heptadione, yield 52%.CN1805916A, which is disclosed, prepares 2,6- dimethyl -3,5- heptan
Diketone, it, by the use of potassium tert-butoxide as catalyst, prepares 3,5- heptadione, yield is 45% under DMF solvent system.
Document J. Am .Chem.soc, 27,1036 (1 962) are reported by the use of NaH as catalyst preparation 2, and 2,6,
6- tetramethyl -3,5- heptadione, reaction yield are relatively low.
J.Org.Chem. 50,26,1985,5598 ~ 5604 preparation 3,5- heptadione are reported.The document is reported, with four
Hydrogen furans is solvent, and under the catalytic action of sodium hydride, ethyl propionate is condensed with methyl ethyl ketone, obtains 3,5 heptadione crude products,
Copper acetate and 3 is recycled, 5 heptan, two intoxicated soft-shelled turtles closed to obtain complex, filtered, and purification, obtains 3,5 heptadione products.In this article
It is ethyl propionate to offer middle report ethyl propionate and the molar ratio of fourth reward:Butanone=1:1. 03, ethyl propionate and sodium hydride rub
Your ratio is ethyl propionate:Sodium hydride=1: 1. 95 .However, since substantial amounts of sodium hydride exists, in actual production, due to big
The sodium hydride unreacted of amount is complete, thus there is danger.In addition, substantial amounts of high-content organic wastewater environment is caused it is unfavorable
Influence, and the cost for producing 3,5 heptadione is also very high.
As can seen above, beta-diketone compound has extensive purposes in chemical and field of medicaments, in the prior art
In, substantial amounts of enterprise and institute have carried out in-depth study to it, however, for being capable of the technique of actual production and
Speech, many problems of generally existing, such as the yield of reaction are relatively low, and it is not high enough to react the purity of products obtained therefrom, in reaction process
There are dangerous destabilizing factor, the waste for reacting generation has environment larger pollution.Therefore, it is still anxious in industrial and industry
A kind of modified preparation process for problem above need to be provided.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the present invention provides a kind of reaction yield and feed stock conversion height, production
Product purity is high, the method for preparing medicine intermediate beta-diketone compound that reaction safety is good and environmental pollution is small.
Technical teaching for solving the problem was
Applicant is had found by the further investigation to correlation technique:During Claisen condensation, highly basic work is generally required
For the catalyst of reaction, highly basic of the prior art is mainly inorganic strong alkali, such as Sodamide, sodium hydride, sodium tert-butoxide, tertiary fourth
Potassium alcoholate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide etc., solvent used are mainly organic inert solvent, such as toluene, chlorine
Benzene, alcohol, aliphatic ether or DMF etc., since dissolubility of the above-mentioned inorganic strong alkali catalyst in organic inert solvent is poor, cause to urge
The ability of change reaction is relatively low, and the selectivity of reaction can also be deteriorated therewith, such as the reaction of methyl propionate and 2- butanone prepares 3,5-
During heptadione, since dissolubility of the catalyst in inert organic solvents is poor, alkali catalyst is caused to activate 2-
1 and the reactive hydrogen of 3 in butanone, so that more accessory substance can be obtained and increase the separating difficulty of reaction.
Based on above-mentioned analysis, the present invention provides a kind of preparation method of beta-diketone compound, the method includes：Formula
II ester compounds of I ketone compound and formula, in organic solvent, in the presence of basic catalyst, reaction obtains beta-diketon chemical combination
Thing III.
R1-CO-CHR2R3Formula I
R4-CO-OR5Formula II
R1-CO-C(R2R3)-CO-R4Formula III
Wherein, R1, R2, R3, R4Separately it is selected from hydrogen, the alkyl of C1 ~ C6（Preferably methyl or ethyl）Or aryl, it is described
Aryl be phenyl or substituted phenyl, R5The independent alkyl selected from C1 ~ C6（Preferably methyl or ethyl）Or aryl.
The organic solvent is inert organic solvents, more preferably benzene, toluene, chlorobenzene, alcohol, aliphatic ether or DMF,
The aliphatic ether is ether, methyl isopropyl ether, methyl tertiary butyl ether(MTBE), glycol dimethyl ether etc.；More preferably methyl
Isopropyl ether, methyl tertiary butyl ether(MTBE), are still more preferably methyl tertiary butyl ether(MTBE), inert organic solvents of the present invention were both
Proton transfer reaction will not be carried out, also solvation does not occur with solute.
It is furthermore preferred that I ketone compound of formula is butanone, and II ester compounds methyl propionate of formula or ethyl propionate, formula III
Beta-diketone compound is 3,5- heptadione.
The basic catalyst is Sodamide, sodium hydride and sodium alkoxide, and the sodium alkoxide is sodium methoxide, potassium methoxide, ethanol
Sodium, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide etc., are preferably sodium tert-butoxide and potassium tert-butoxide, more preferably potassium tert-butoxide.Alkalescence
The molar ratio of catalyst and I ketone compound of starting materials of formulae is 1:1-3, is preferably 1:1-1.5.
During ester is added, generated beta-diketon chemical combination is removed by distilling typically under the conditions of solvent refluxing
Thing.Therefore the method reaction temperature of the Claisen condensation is preferably at least 15 DEG C higher than the boiling point of the alcohol.Reaction temperature is at least 30 DEG C.
The present invention a kind of particularly suitable embodiment in, range of reaction temperature be 35 DEG C to 200 DEG C, with 40 DEG C to 150 DEG C compared with
Good, pressure is normal pressure.Pressure is not not extremely important for this method, but selects specified pressure to promote to a certain extent
The quick removal of the product dione compounds produced into reaction medium.If reaction carries out under reduced pressure, convenient is anti-
Temperature model is answered because of 30 DEG C to 140 DEG C.
The molar ratio of II ester compounds of I ketone compound of formula and formula is preferably less than 1, is preferably 1:1.1-5 more preferably 1:1.2-
4.In general, ester is than ketone excess 10-300%.
In terms of existing technologies, acquirement has the beneficial effect that the present invention：
1st, present invention employs specific catalyst potassium tert-butoxide and specific reaction dissolvent methyl tertiary butyl ether(MTBE), due to the tert-butyl alcohol
The organic group of potassium is larger can be preferably among solvent, and methyl tertiary butyl ether(MTBE) has relatively large polarity, can be preferable
Ground catalyst-solvent potassium tert-butoxide, and reaction raw materials ketone compound and ester compounds also can be preferably dissolved, so as to improve
The homogeneity of reaction system, avoids in reaction system because deliquescent problem, so as to produce a large amount of accessory substances, effectively carries
The high selectivity and reaction yield of product, reaction yield can reach 72.4%, while reduce the difficulty of post-reaction treatment,
The pollution to environment is reduced, greatly reduces production cost, improves the economic efficacy of production.
2nd, due to reaction used by catalyst be potassium tert-butoxide, avoid Sodamide used in the prior art, hydrogen
Change the catalyst of the highly dangerous such as sodium, improve the security of production, reduce the requirement to consersion unit etc., so as to drop
The cost of low production.
Embodiment
The preparation process of the present invention is further described below by way of exemplary embodiment.But these embodiments are only
For illustrating the present invention, any restrictions are not formed to the scope of the present invention.It will be apparent to a skilled person that not
In the case of deviateing the spirit and scope of the present invention, technical scheme and its embodiment can be carried out a variety of
Equivalence modification, replace and change, these should all fall within the scope of protection of the present invention.
Embodiment 1
In three-necked flask, by 11.2g potassium tert-butoxides（0.1mol）Add in 50mL anhydrous methyl tertbutyl ethers, heating stirring is returned
Stream 30 minutes, cools to 35 DEG C, 0.3mol methyl propionates and 0.1mol butanone is slowly added drop-wise in reaction bulb successively, added
When reaction 2 is small after complete.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, reaction solution neutral with dilute hydrochloric acid tune pH value
Stratification, separates organic layer, and to organic layer knowable to gas-chromatography is analyzed, product 3, the reaction yield of 5- heptadione is
72.4%（In terms of butanone）.
Embodiment 2
In three-necked flask, by 11.2g potassium tert-butoxides（0.1mol）Add in 50mL anhydrous ethers, heating stirring flows back 30 points
Clock, cools to 35 DEG C, and 0.3mol methyl propionates and 0.1mol butanone are slowly added drop-wise in reaction bulb successively, reacted after adding
2 it is small when.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, neutral with dilute hydrochloric acid tune pH value, reaction solution, which is stood, to be divided
Layer, separates organic layer, and to organic layer knowable to gas-chromatography is analyzed, product 3, the reaction yield of 5- heptadione is 44.6%
（In terms of butanone）.
Embodiment 3
In three-necked flask, by 11.2g potassium tert-butoxides（0.1mol）Add in the anhydrous diethylene glycol dimethyl ethers of 50mL, heating stirring
Reflux 30 minutes, cools to 35 DEG C, 0.3mol methyl propionates and 0.1mol butanone is slowly added drop-wise in reaction bulb successively,
When reaction 2 is small after adding.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, reaction neutral with dilute hydrochloric acid tune pH value
Liquid stratification, separates organic layer, to organic layer knowable to gas-chromatography is analyzed, product 3, and the reaction yield of 5- heptadione
For 62.3%（In terms of butanone）.
Embodiment 4
In three-necked flask, by 11.2g potassium tert-butoxides（0.1mol）Add in 50mL dry ethylene glycol dimethyl ethers, heating stirring is returned
Stream 30 minutes, cools to 35 DEG C, 0.3mol methyl propionates and 0.1mol butanone is slowly added drop-wise in reaction bulb successively, added
When reaction 2 is small after complete.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, reaction solution neutral with dilute hydrochloric acid tune pH value
Stratification, separates organic layer, and to organic layer knowable to gas-chromatography is analyzed, product 3, the reaction yield of 5- heptadione is
58.7%（In terms of butanone）.
Embodiment 5
In three-necked flask, by 11.2g potassium tert-butoxides（0.1mol）Adding in 50mL anhydrous benzenes, heating stirring flows back 30 minutes,
35 DEG C are cooled to, 0.3mol methyl propionates and 0.1mol butanone are slowly added drop-wise in reaction bulb successively, react 2 after adding
Hour.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, reaction solution stratification neutral with dilute hydrochloric acid tune pH value,
Organic layer is separated, to organic layer knowable to gas-chromatography is analyzed, product 3, the reaction yield of 5- heptadione is 38.9%（With
Butanone meter）.
Embodiment 6
In three-necked flask, by 11.2g potassium tert-butoxides（0.1mol）Add in 50mL anhydrous DMFs, heating stirring flows back 30 points
Clock, cools to 35 DEG C, and 0.3mol methyl propionates and 0.1mol butanone are slowly added drop-wise in reaction bulb successively, reacted after adding
2 it is small when.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, neutral with dilute hydrochloric acid tune pH value, reaction solution, which is stood, to be divided
Layer, separates organic layer, and to organic layer knowable to gas-chromatography is analyzed, product 3, the reaction yield of 5- heptadione is 46.2%
（In terms of butanone）.
Embodiment 7
In three-necked flask, by 9.6g sodium tert-butoxides（0.1mol）Add in 50mL anhydrous methyl tertbutyl ethers, heating stirring is returned
Stream 30 minutes, cools to 35 DEG C, 0.3mol methyl propionates and 0.1mol butanone is slowly added drop-wise in reaction bulb successively, added
When reaction 2 is small after complete.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, reaction solution neutral with dilute hydrochloric acid tune pH value
Stratification, separates organic layer, and to organic layer knowable to gas-chromatography is analyzed, product 3, the reaction yield of 5- heptadione is
60.8%（In terms of butanone）.
Embodiment 8
In three-necked flask, by 8.4g potassium ethoxides（0.1mol）Add in 50mL anhydrous methyl tertbutyl ethers, heating stirring reflux
30 minutes, 35 DEG C are cooled to, 0.3mol methyl propionates and 0.1mol butanone are slowly added drop-wise in reaction bulb successively, added
When reaction 2 is small afterwards.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, neutral with dilute hydrochloric acid tune pH value, reaction solution is quiet
Layering is put, separates organic layer, to organic layer knowable to gas-chromatography is analyzed, product 3, the reaction yield of 5- heptadione is
52.6%（In terms of butanone）.
Embodiment 9
In three-necked flask, by 2.4g sodium hydrides（0.1mol）Add in 50mL anhydrous methyl tertbutyl ethers, heating stirring reflux
30 minutes, 35 DEG C are cooled to, 0.3mol methyl propionates and 0.1mol butanone are slowly added drop-wise in reaction bulb successively, added
When reaction 2 is small afterwards.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, neutral with dilute hydrochloric acid tune pH value, reaction solution is quiet
Layering is put, separates organic layer, to organic layer knowable to gas-chromatography is analyzed, product 3, the reaction yield of 5- heptadione is
46.%（In terms of butanone）.
Embodiment 10
In three-necked flask, by 3.9g Sodamides（0.1mol）Add in 50mL anhydrous methyl tertbutyl ethers, heating stirring reflux
30 minutes, 35 DEG C are cooled to, 0.3mol methyl propionates and 0.1mol butanone are slowly added drop-wise in reaction bulb successively, added
When reaction 2 is small afterwards.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, neutral with dilute hydrochloric acid tune pH value, reaction solution is quiet
Layering is put, separates organic layer, to organic layer knowable to gas-chromatography is analyzed, product 3, the reaction yield of 5- heptadione is
48.7%（In terms of butanone）.
Embodiment 11
In three-necked flask, by 11.2g potassium tert-butoxides（0.1mol）Add in 50mL anhydrous methyl tertbutyl ethers, heating stirring is returned
Stream 30 minutes, cools to 35 DEG C, 0.3mol methyl propionates and 0.1mol butanone is slowly added drop-wise in reaction bulb successively, added
When reaction 2 is small after complete.Then room temperature is cooled to, 30mL water is added dropwise under the protections of N 2, reaction solution neutral with dilute hydrochloric acid tune pH value
Stratification, separates organic layer, and to organic layer knowable to gas-chromatography is analyzed, product 3, the reaction yield of 5- heptadione is
72.4%（In terms of butanone）.
The reaction yield situation of 1 different catalysts of table and inert organic solvents
| Catalyst | Inert organic solvents | Reaction yield（%） |
| Potassium tert-butoxide | Methyl tertiary butyl ether(MTBE) | 72.4 |
| Potassium tert-butoxide | Ether | 44.6 |
| Potassium tert-butoxide | Diethylene glycol dimethyl ether | 62.3 |
| Potassium tert-butoxide | Glycol dimethyl ether | 58.7 |
| Potassium tert-butoxide | Benzene | 38.9 |
| Potassium tert-butoxide | DMF | 46.2. |
| Sodium tert-butoxide | Methyl tertiary butyl ether(MTBE) | 60.8 |
| Potassium methoxide | Methyl tertiary butyl ether(MTBE) | 52.6 |
| Sodium hydride | Methyl tertiary butyl ether(MTBE) | 46.3 |
| Sodamide | Methyl tertiary butyl ether(MTBE) | 48.7 |
By table 1 it can be found that catalyst potassium tert-butoxide is in the presence of methyl tert-butyl ether solvent, product 3,5- heptadione
Product yield highest can reach 72.4%, reason be probably due to dissolubility of the organic catalyst in organic inert solvent compared with
Difference, the local concentration of catalyst is excessive, and raw material 2- butanone, methyl propionate and product 3, and there are at least one in 5- heptandiols
Reactive hydrogen, that is, may produce different accessory substances in reacting, therefore, higher selectivity can be obtained to this in initial reaction stage
Reaction is directly perceived important, and creatively selection solves this well with the combination of potassium tert-butoxide and methyl tertiary butyl ether(MTBE) in the present invention
Problem, the selectivity and product yield of reaction are greatly improved.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (7)
1. a kind of preparation method of medicine intermediate beta-diketone compound, the described method includes：I ketone compound of formula and formula II are esterified
Compound, in organic solvent, in the presence of basic catalyst, reaction obtains III beta-diketone compound of formula,
R1-CO-CHR2R3Formula I,
R4-CO-OR5Formula II,
R1-CO-C(R2R3)-CO-R4Formula III,
Wherein, R1, R2, R3, R4Separately it is selected from hydrogen, the alkyl of C1 ~ C6（Preferably methyl or ethyl）Or aryl, R5It is independent
The alkyl selected from C1 ~ C6（Preferably methyl or ethyl）Or aryl, it is characterised in that：The organic solvent is organic for inertia
Solvent, more preferably benzene, toluene, chlorobenzene, alcohol, aliphatic ether or DMF, the aliphatic ether for ether, methyl isopropyl ether,
Methyl tertiary butyl ether(MTBE), glycol dimethyl ether etc.；More preferably methyl isopropyl ether, methyl tertiary butyl ether(MTBE), it is further excellent
Elect methyl tertiary butyl ether(MTBE) as, the basic catalyst is Sodamide, sodium hydride or alkoxide.
A kind of 2. preparation method of beta-diketone compound according to claim 1, it is characterised in that:The inertia is organic molten
Agent will not both carry out proton transfer reaction, also solvation not occur with solute.
A kind of 3. preparation method of beta-diketone compound according to claim 1, it is characterised in that:The inertia is organic
Solvent is methyl tertiary butyl ether(MTBE).
A kind of 4. preparation method of beta-diketone compound according to claim 1, it is characterised in that：The alkoxide is first
Potassium alcoholate, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert-butoxide etc., are preferably sodium tert-butoxide or potassium tert-butoxide, more preferably tertiary fourth
Potassium alcoholate.
A kind of 5. preparation method of beta-diketone compound according to claim 1, it is characterised in that:Reaction temperature is at least
For 30 DEG C, preferable reaction temperature scope is 35 DEG C to 200 DEG C, and pressure is normal pressure.
A kind of 6. preparation method of beta-diketone compound according to claim 1, it is characterised in that:I ketone compound of formula and
The molar ratio of II ester compounds of formula is preferably less than 1, is preferably 1:1.1~5.
A kind of 7. preparation method of beta-diketone compound according to claim 1, it is characterised in that:I assimilation of formula
Compound is butanone, II ester compounds methyl propionate of formula or ethyl propionate, and III beta-diketone compound of formula is 3,5- heptadione.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810019861.2A CN108002996A (en) | 2018-01-09 | 2018-01-09 | A kind of preparation method of medicine intermediate beta-diketone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810019861.2A CN108002996A (en) | 2018-01-09 | 2018-01-09 | A kind of preparation method of medicine intermediate beta-diketone compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108002996A true CN108002996A (en) | 2018-05-08 |
Family
ID=62050424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810019861.2A Pending CN108002996A (en) | 2018-01-09 | 2018-01-09 | A kind of preparation method of medicine intermediate beta-diketone compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108002996A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0454624A1 (en) * | 1990-04-26 | 1991-10-30 | Ciba-Geigy Ag | Process for the production of 1,3-diketones |
| CN107324985A (en) * | 2016-04-29 | 2017-11-07 | 中国石油化工股份有限公司 | A kind of preparation method of beta-diketone compound |
-
2018
- 2018-01-09 CN CN201810019861.2A patent/CN108002996A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0454624A1 (en) * | 1990-04-26 | 1991-10-30 | Ciba-Geigy Ag | Process for the production of 1,3-diketones |
| CN107324985A (en) * | 2016-04-29 | 2017-11-07 | 中国石油化工股份有限公司 | A kind of preparation method of beta-diketone compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Heck | Acylation, methylation, and carboxyalkylation of olefins by Group VIII metal derivatives | |
| Dong et al. | Synthesis of chalcones via Claisen–Schmidt condensation reaction catalyzed by acyclic acidic ionic liquids | |
| Chen et al. | A practical palladium catalyzed dehalogenation of aryl halides and α-haloketones | |
| EP2891646B1 (en) | Method for producing a-fluoroacrylic acid ester | |
| CN104203884A (en) | Passivation of a homegeneous hydrogenation catalyst for the production of ethylene glycol | |
| US8766015B2 (en) | Method for preparing a glycol mono-tertiary-butylether compound | |
| Yadav et al. | Ring opening of epoxides with alcohols using Fe (Cp) 2BF4 as catalyst | |
| Firouzabadi et al. | Facile preparation of symmetrical and unsymmetrical ethers from their corresponding alcohols catalyzed by aluminumdodecatangstophosphate (AlPW12O40), as a versatile and a highly water tolerant Lewis acid | |
| Pericas et al. | Zinc (II) oxide: an efficient catalyst for selective transesterification of β-ketoesters | |
| US20140024854A1 (en) | Process for preparing carboxylic acid esters | |
| KR102096917B1 (en) | Process for the preparation and work-up of a reaction mixture containing triacetone amine | |
| Chen et al. | A New Aspect of Magnesium Bromide‐Promoted Enantioselective Aryl Additions of Triaryl (tetrahydrofuran) aluminum to Ketones Catalyzed by a Titanium (IV) Catalyst of trans‐1, 2‐Bis (hydroxycamphorsulfonylamino) cyclohexane | |
| US9950984B2 (en) | Production method for alpha-fluoro acrylic acid esters | |
| JP6200417B2 (en) | Method for producing hydroxyphenylcyclohexanol compound | |
| CN109535120B (en) | Preparation method of 7-substituted-3, 4,4, 7-tetrahydrocyclobutane coumarin-5-ketone | |
| CN108002996A (en) | A kind of preparation method of medicine intermediate beta-diketone compound | |
| AU651235B2 (en) | Chemical process | |
| GB2023577A (en) | Process for producing benzyl alcohol and substituted benzyl alcohols | |
| CN105481702B (en) | The method of one pot process m-phenetidine | |
| CN107879919A (en) | A kind of preparation method of the heptadione of medicine intermediate 3,5 | |
| CN109438402B (en) | Benzofuranone derivatives and synthesis method thereof | |
| CN101003456B (en) | Method for preparing Beta, Gamma unsaturated ester | |
| US20130123516A1 (en) | Novel phosphine-based catalysts useful for the telomerization of butadiene | |
| JP2005247840A (en) | Process for producing 1,3-propanediol and 1,3-propanediol obtained by the same process for production | |
| CN101343213B (en) | Allyl ether series compound and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180508 |
|
| RJ01 | Rejection of invention patent application after publication |